Condensation of alcohols in the presence of calcium hydroxide



'c ALCOHOL mooucr ALCOHOLS INCLUDING GEM/ALCOHOL INVENTOR.

NE ON E. E. BURGOYNE CONDENSATION 0F ALCOHOLS IN THE PRESENCE OF CALCIUM HYDROXIDE Filed Oct. 1, 1951 EOE YEOK OWN-N HE A VIE P PRODUC 7'5 NEON EOR YENOOQQ; E

f C ALCOHOL COMPRESSOR 7 NE ON July 14, 1953 EOR RWENOEOO c ALCOHOL E51 Burgoyne SEPA RA r/o/v z0/v HEA V/ER ppooucrs ZONE C ONDE MS'A T/ON C ALCOHOL c, ALCOHOL] Patented July 1 4, 1 953 CONDE NSATION OF ALCOHOLS IN THE. PRESENCE OF CALCIUM HYDROXIDE Edward E. Burgoyne, Bartlesville, kla.,. assignor Company; a; corporation to Phillips Petroleum of Delaware Application October'l, 1951, SeriaINo. 249,092 1'7 Claims. (Cl. 260-'-618) This invention relates to the condensation of a lower molecular weight alcohol to forma higher molecular weight alcohol. In one aspect, it relates to the condensation of a lower molecular weight alcohol to form a higher molecular weight alcohol in which the number of carbon atoms is a nonintegral multiple of that in'the original alcohol. In another aspect, it relates to the condensation of an alcohol containing at least two carbon atoms per molecule to form an alcohol containin one less than twice the number of carbon atoms per molecule of theorigina-l' alcohol. In still another aspect, it relates to the intercondensation of a primary straight-chain alkanol with a branched-chain alkanol. In a further aspect, it relates to the intercondensation-of a primary straight-chain alkanol with an aromatic alcohol. In still another aspect, the invention relates to conductingthe above-mentioned condensations in the presence of certain contact materials and under certain conditions of temperature and pressure.

This application is 'a' continuation-in-part of copending application Serial Number 133,037 filed December 1949, now abandoned.

According to this invention,-a low-boiling primary straight-chain alkanol is condensed in the presence of a contact material comprising calcium hydroxide to obtain a higher-boiling alcohol in which the number of carbon atoms per molecule is a nonintegral multiple of that in the original alcohol. Inone embodiment of this invention, two moles of a normal l-alkanol condense to form a higher-boiling'alkanol'in' which the number of carbon atoms isa nonintegral multiple of that in the original l-alkanol. In another embodiment, two different normal I- alkanols intercondense to form ahigher-boiling alkanol. In another embodiment, a normal 1- alkanolintercondenses with a'branched-chain alkanol to form a higher-boiling alkanol. In still another embodiment, a normal l-alkanol intercondenses with an aromatic alcohol to form an aryl-substituted. alkanol; In a preferred embodiment, the calciumhydroxideis promoted witha minor proportion of at least one of an alkalimetal hydroxide, silica, and magnesia. In another preferred embodiment the contact material is a mixture of calcium hydroxide, preferably soda-lime, and copper oxide-chromium oxide (copper-chromite). The condensations of this. invention. areconducted at a. temperature in the. range of 375 to 58.0" C. when calcium. hydroxide or soda-lime is used as. thecontact material and. at. temperatures of 300? to 5809-16. when a. mix-. ture of soda-lime. and copper oxide-chromium oxideisused. J

. atoms per molecule.

, intercondensation with. a normal l-alkanol.

- nol, propanol has been condensed to hexanol, etc.

The number of carbon atoms in the condensation products of the invention, letting 11.. equal the numberof carbon atoms per molecule of original alcohol, can be represented by Zn-l.

- Thus, the. following reactions indicate the nature of the condensations effected according to this invention.

In other terms, 2 moles of reactant propanol condense to give a C alcohol.

Likewisecrmolesoi ethanol (n.=2) condense The alcohols with, which this invention is primarily concerned are. the normal or straightchain. l-alkanols having from 2 to 10 carbon Branched-chain alkanols do not undergo the reaction of this invention by themselves. However, I have discovered that, in admixture with a normal l-alkanol, a branchedchain alkanol undergoes cross-condensation or For example, 2-methyl-l-propanol does not condense with itself, but, in admixture with l-propanol, intercondenses with the l-propanol to form 2- methyl-3-ncntano1.

Furthermore, I have discovered that aromatic alcohols, such as benzyl alcohol, do not condense alone, but that, inadmixture with l-propanol, benzyl alcohol intercondenses to form Z-benzyllpropanol.

To recapitulate, then, the feed materials of this invention. include (1) the normal l-alkanols having from two to, ten carbon atoms per molecule, (2) branched-chain alkanols of the same molecular weight range, and (3) aromatic alkanols of the type of benzyl alcohol and its homologues, such as 2:-phenyl ethanol, etc, having from seven to ten. carbon atoms. per molecule. The second and the. third types of alcohols are never used individually, but always in admixture with the first.

The contact. material according to this inventionis. essentially calcium hydroxide and is preferably promoted withminor amounts of an alkalimetal hydroxide, such as sodium or potassium hydroxide, and silica. The proportion of alkalimore preferably not more than 15 per cent of";

magnesium hydroxide. avery satisfactory contact material v I have found that aliphatic alcohols, particularly the primary alcohols, 'oangbe condensedqin Commercial soda-lime is 4- granular soda-lime. The mechanical mixture can be employed in the granular form or it can be pilled or pelleted by any of the Well known methods. In the process the mixed catalyst contains copper oxide and chromium oxide in weight ratios within the range of 0.2:1 to 1:1,.and the catalyst contains from to 50 weight per cent 1 of copper oxide-chromium oxide and from 50 to the presence of soda-lime orsoda-lime-in admixa x ture with copper oxide-chromium oxide as a contact material to form highen-boiling aliphatic;

alcohols, and, as a result of the presence 'of the soda-lime, an alcohol containing one less than twice the number of carbon atoms in the original or uncondensed alcohol is produced.

When soda-lime,.not in admixture with copper oxide-chromium oxide, isemployed as a contact material, the condensationreaction takes place in accordance with the equation However, when a mixture of-soda-lime and copper oxide-chromium oxide is employed, not onlyv does reaction ('2) take place, but, simultaneously therewith, a second condensation reaction takes place in accordance with the equation wherein the number of carbon atoms in the product alcohol is equal to the sum of; the number of carbon atoms in the reactant alcohols, Thus, when propanolis condensed inthe presence of soda-lime alone, the reaction proceeds 'in accordance with Equation 2,12 being *equal to y, anda C5 alcohol, viz diethyl carbmol is produced.

However, when propanol iscondensed in the presenoe of a mixture of soda-lime and copper oxidechromium oxide (zr y), the reaction proceeds in accordance with Equations -2 and 3, and a C5 and a C6 alcohol, viz diethyl carbinal and 2- methylpentanol-l, are produced.

In Equations 2 and 3, and y are preferably integers within the range of 2 to 10, but alcohols containing more than 10 carbon atoms per molecule are within the scope ofthe invention. Specific alcohols that may be employed in the process are ethanol, propanol, butanol, pentanol, hexanol, and higher alcohols and their corresponding isomers. Mixtures of propanol and"but'a-nol, butanol and pentanol, and propanol andhexanol may be condensed in accordance with theinvention. These specific mixturesere merely illustrative of the various mixtures of alcohols'that are within the scope of the invention.

The copper oxide-chromium oxide accordingto this invention can be prepared --inany suitable 95 weight per cent soda-lime.

The temperature at which the condensation reaction'is effected is dependent upon the contact ,material employed. When employing soda-lime,

not in-admixture with copper oxide-chromium oxide, a temperature of at least 375 C. and preferably not above 580 C. is effective. Data in this specification show that, with this type of contact material, a temperature below 375 C.,

and particularly 350 (3., produced little or no conversion. However, when soda-lime is employed in admixture with copper oxide-chromium oxide, temperatures as low as 300 C. produce satisfactory yields of high-boiling alcohols, but

- the, higher temperatures within the range of 3'75 to 580 C. can also be used with this latter type of contact material, if desired. The effect of the copper oxide-chromium oxide is to enable the use of a lower temperature for the condensation reaction. The production of some alcohols containing'twice the number of carbon. atoms in the original'alcohol, e. g. 2-methylpentanol-1 from normal propanol, takes place in the presence of a catalyst containing both soda-lime and copper oxide-chromium oxide;

At the temperatures disclosed above, the reactant alcohols are in the gaseous phase, and the-condensation reaction is effected with the reactants'in this phase. The gases of the reactant alcohols arecontacted with a bed of one of the above described contact materials at a charge rate within the range 'of lfto 15, preferably 2 to 10, moles of, reactant alcohol. per kilogram of contact material per hour. j

The condensation may be conducted at pressures of 0 to 1 000 p. s. 1., preferably 0 to 750 p. s. i. andmore preferably 200 to 600 p. s. i.

The condensation reaction yields not only higher-boiling alcohols, but also reaction byproducts, such as hydrogen, carbon dioxide, carbon; monoxide, both saturated. and unsaturated aldehydes andketones, dialkyl ethers and esters. To; simplif y the separation of the alcohols from thQ'IBZtQlSlOII eiiluent, to improve the yield of the I higherv boiling alcohols, and to recover the maxi- '"-mum amount of uncondensed starting alcohols for reuse in the condensation reaction zone, the mixtureof products from the condensation step is subjected to hydrogenation conditions, and the hydrogen from the condensation step is utilized for'the hydrogenation reaction. A method of carrying out our overall process is set forth in detail subsequently.

The accompanying drawing is a schematic diagram showing two embodiments of this invention. i

Referring'now to Figure 1, an aliphatic alcohol, such as normal propanol, is introduced via line I to condensation zone 2 where the alcohol is contacted with-one of the contact materials and at the conditions previously described. The reactioneflluent containing product alcohols, aldehydes, ketones, hydrogen, and other reaction productsis withdrawn via line 3 to compressor lwhere the efiiuent is compressed from atmospheric pressure to a pressure within the range of 25 to 1000 pounds per square inch. The comaci -ear:

pressed efiiuent is then. passedwia: line .iwto? bye.

drogenation zone 6: where: the eflluen't ispassed into contact with a hydrogenation catalyst, such as Raney nickel, metallic nickel: 'on an inert sup port such as kieselguhr, copper oxide-chromium, oxide, and the like at a temperaturepf to, 200 C. The effluent from zone. B is withdrawn via line 7 into fractionator 8 where the .efllil underoges fractional distillation. ,liydrogen isj withdrawn from fractionator B and recycled. via. line 9 to compressor 4 for use in hydrogenation zone 6, and any hydrogen not re uiredingzone 6 is withdrawn from the system via Water and light ends are withdrawn via line II,

and uncondensed starting alcohol is withdrawn from fractionator 8 and recycled to zone 2 via line l2. The high-boilingalcohols produced in the process are withdrawn'via 1ines'-|a and H" and the fractionation residues "or-bottomsprod-' nets are withdrawn via line [5.

The following specific examples are illustrative of this invention.

Example I 200 grams (3.3 moles) of normal propanol were passed through a Pyrex reaction tube,.1 inches long and one inch in diameter, containing a mixture of 30 grams of copper oxidechromium oxide and 70 grams of soda-lime at 350 C., at mospheric pressure, and an hourly gaseous space velocity of 90 to 120. From the condensation step, 0.68 mole of hydrogen per mole of normal propanol was evolved, and the condensation reaction efiluent Was passed over a Raney nickel.

catalyst at to 150 C. and at a pressure of 200 p. s. 1. Reaction products from the hydro genation step consumed 0.17 moleof hydrogen. per mole of original normal propanol; and the resulting product was fractionally distilled to yield 11.4 per cent water, 40.8 per cent normal propanol, 7 .1 per cent di-n-propyl ether, 14 per cent diethyl carbinol, 14 per cent 2-methylpentanol-l, and 12.7 per centhigher: boiling residue. I

. Example II The procedure disclosed inv Example Twas em.-

ployed with soda-lime, containing no admixed" copper oxide-chromium oxide, as a contact ma-' At a temperature of 350 C.'no conden terial. sation of the normal propanol occurred. At a. temperature of 400 C. the reaction product contained per centdiethylcarbinol and no Csalcohols. M 1 1 These experimental data show thatattempera tures below 400 C. soda-lime, containing :no.

copper oxide-chromium oxide, effects: substantially no condensation of aliphatic alcohols,=and,

at temperatures of 400 Ci and higher, this contact material effects a condensation of an alcohol to form a higher-boiling alcoholcontaining one less than twice the number of carbon atoms in the reactant alcohol. The data in-Examplesl' and II show that, by the use-of a mixture of copper oxide-chromium oxide and soda-limejt-he condensation of alcohols canb'e efiected at temperatures lower than thoserequired when soda:

lime containing no copper oxide-chromium oxide; is employed.

In the foregoing description of the drawing. I

have disclosed the condensationjof an alcohol.- followed by hydrogenation of resulting products with hydrogen produced in the condensation step to increase the yield of condensed alcohols. However, in a second embodiment of this invention, shown in Figure z, the -separate hydrogen- 6. ation step-is eliminated, and the effluent from the condensation step is passed directly to a separation zone, such as fractionation zone 8. In this embodiment, the/condensation step is effected; at a pressure above atmospheric and within the range of 25 to 1000, preferably 200 to 600 p. s. i.,v and the other reaction conditions in the conv densation zone are similar to those described hereinabove. Ordinarily, the reaction is efiected in the gaseous phase, but liquid phase and mixed gaseous and liquid phases may be employed effected in the condenstation zone without the addition of hydrogen from an outside source.

W As shown in Equation 2, hydrogen is produced during the condensation reaction when soda-lime is present in the catalyst, and this hydrogen is employed to effect the hydrogenation reaction. This second embodiment eliminates the hydrooverhead from fractionation zone 8 may be recycled through conduit 9 to condensation zone 2 to facilitate the hydrogenation reaction.

. genation zone, and hydrogen, obtained as an,

The following example is illustrative of the second embodiment of this invention.

Example III 1032 grams of soda-lime of 4- to 8-mesh size and containing 2 per cent moisture was placed in a steel reaction tube. Normal propanol was passed through the catalyst in the vapor phase at a charge rate of 7.07 moles of alcohol per kilogram ofsoda-lime per hour. The reaction temperature was 400 C., the reaction pressure was 600 p. s. i., and the reaction was continued for a period of 5.67 hours.v From the reaction zone 0.687 mole of gaseous efiluent per mole of propanol was evolved, and this gas contained 87.6 per cent hydrogen. The liquid reaction product was fractionally distilled to yield 2.37 per cent light ends, 4.85 per cent water, 61.0 percent normal propanol, 23.2 per cent diethyl carbinol, 3.9 per cent Z-methyl pentanol-l and 4.75 per cent higher-boiling residue.

The following example demonstrates the operability of my invention for the condensation of li-octanol.

Example, IV

.1-octanol was passed over soda-lime at 400 C. and 600 p. s. i. at a rate of 2.8 moles per kilogram ofsoda-lime'per hour. Gasevolution was 0.766 mole/mole octanol. The liquid recovery was 90.5 weight per cent. The liquid product was collected in two equal portions, and these were found to have substantially identical compositions viz; i

Weight per cent Water 4.6 Light ends 3.4 Octene 1.7- Qctanol 59.0 8-pentadecano1 29.9 Residue 1.4

. The 8--pentadecanol was a nearly white solid melting at 43* to- 46 C. A portionwas fied by recrystallizatiomand the melting point. was determined tobe 49 to 50 C. The litera--. ture value for the melting point of B-pentadecanol is 49 to 50 C. As a further proof of identity, 1

gram was oxidized with dilute aqueous acidic potassium dichromate. There was obtained 0.5 gram of 8-pentadecanone, melting at 39 to 40. C. The literature value for the melting point of this ketone is 40 C.

In like manner, l-pentanol is converted to a C9 alkanol.

. Example V Water 1.9 Light ends 6.6 l-propanol 59.3 3-pentanol (diethyl carbinol) 15.8 2-methyl-1-pentanol s 1 9.2 Residue 7.2

Comparison of the data above with those in Example III show the promoting effect of the'constituents of soda-lime other than calcium hydroxide. For example, when soda-lime was used, as in Example 111, only 3.9 per cent of the liquid product was 2-methyl-1:\entanol1 (Cs), whereas, when chemically pure calcium hydroxide was used, as in the present example, the liquid product contained 9.2 per cent of 2-methyl-l-pentanol (Cs). Also, the high-boiling residue formed in the present example amounted to 7.2 per cent of the liquid product whereas in ExampleIII, where soda-lime was used, the high-boiling residue amounted to only 4.75 per cent of the liquid product.

Example VI Water v 8.7

Benzene 4.3 l-propanol 19.3 3-pentano1 2.5 2-methyl-1-pentanol 1.1 Toluene "4.8 Benzyl alcohol 21.6 Benzaldehyde 4.9 2-benzyl-1-propanol 8.9 Heavier 23.9

An appreciable yield of 2-benzyl-1-propanol was formed by intercondensation- Benzyl alco-- hol alone fails to react under the same conditions. 1

Example VII A mixture of 32 weight per cent l-propanol-and 68 weight per cent l-octanol was contacted with soda-lime at 400 C. and 40 atmospheresat a Gaseous products amounting to 051' Weight per cent 8 chargeirate of 3.3 moles'per kilogram of soda-lime perhour; The product liquid amounted to weight percent offthe charge and had the following composition, in weight per cent:

Water 1.8 Light 1ends 10.6 Unreacted 1propan0l 10.9 3'-pentanol s 5.5 2 methyl-1-pentano1 2.8 Unrleacted '1-octanol 34.1 3 decan'o1 r. 14.6 8{perita'decanol 17.4 H'eaVierf Z-"r; 2.3

The B-decanolisbelieved to have been formed by the intercondensation ofl-propanol with 1- octanol according to Equation 2. The 3-pentanol is believed to have been formed by condensation o f two molesof l-propanol in accordance with Equation 1. The 8-pentadecan0l is believed to have been formed by the condensation of two moles of l-octanol in accordance with Equation 2.

: Example VIII A'mixture of 45 weight per cent l-propan-ol and 55 weight percent"2-methyl-l-propanol was contacted with soda-lime at 400 C., 40 atmospheres, and a charge rate of 8.6 moles per kilogram sodalime per hour. The product liquid amounted to 87 weight per cent of the charge and had the following composition, in weight per cent:

by the condensation of l-propanol in accordance with Equation 1. The 2-methyl-3-pentanol is be lievedto have been formed by intercondensation of the l-propanol with the Z-methyl-l-propanol in accordance with Equation 2. 2-methyl-lpropanol alone does not react under the same conditions.

Example IX l-butanol was contacted with soda-lime at 400 C., 40 atmospheres, and a charge rate of 7.3 moles per kilogram soda-lime per hour. The chief product was 4-heptanol, which has one less than twice the number of carbon atoms per molecule that lebutanol has. q

kpropanol was contacted with soda-lime contain-ing. 1 9,4 per cent magnesia at 400 0., 40 atmospheres, and a charge rate of 7.3 moles per kilogram soda-lime per hour} The product liquid amounted to 87 weight per cent of the charge and had theiollowing composition in weight per cent:

Wate1" 4.6 Light ends -L 3.7 Unreacted l-propanol 73.2 3-pentanol- 12.7 Z-methyl-l-pentanol 4.2 Heavier 1.6

H M 100.0 .The ma nesia h d the [e c or increasing t e enemas-z '9 yield of 2-methyl-1-pentanol (Cs) according to Equation 3. r I mam ze'xr v A number of other oxides and several silicates were tested to determine whether they would promote the alcohol condensation reactions in accordance with the present invention. Materials tested for this purpose were magnesium oxide, chromic oxide, sodium silicate, calcium silicate, calcium borosilicate, calcium phosphatesilicate, thorium dioxide and copper-chromium oxide. The alcohol us'ed'in these tests was 1- propanol. In only one case, i. e., magnesia, was any 3-pentanol produced, and in this case the 3-pentanol amounted to only 2.3 weight per cent of the product liquid; 74.4 per cent of the product liquid was unreacted l-propanol. These tests were conducted at approximately .400 C. and 600 p. s. i.

The soda-lime used in Examples I to IX was essentially calcium hydroxide containing 1.0 Weight per cent magnesia, 0.7 weight per cent sodium hydroxide, 0.6 weight per cent silica, and 2.1 weight per cent water. That in Example X contained 19.4 weight per cent magnesia, 0.9 per cent sodium hydroxide, and 13.4 weight per cent water.

The term contact material as used herein is intended to cover both catalytic and reagent functions of the calcium hydroxide, since the function of the calcium hydroxide does not appear to be purely catalytic, but may also be that of a chemical reagent.

In copending application Serial 249,227, filed October 1, 1951, a process for the condensation of alkanols in the presence of calcium oxide is disclosed and claimed.

Reasonable variation and modification are possible within the scope of the foregoing disclosure and the claims to the invention, the essence of which is that a normal primary C2 to C alkanol is condensed, with itself or with an alcohol selected from the group consisting of branchedchain, primary alkanols having two to ten carbon atoms per molecule, and aromatic alcohols of the type of benzyl alcohol and its homologues having seven to ten carbon atoms per molecule, to obtain a higher alcohol containing a nonintegral multiple of the number of carbon atoms of the original alkanol by contacting with calcium hydroxide, preferably promoted with sodium hydroxide, at 375 to 580 C.; and that, by further promoting the calcium hydroxide with copper oxide-chromium oxide, the condensation may be conducted at temperatures as low as 300 C.

I claim:

1. A process for converting a lower molecular weight, normal, primary alkanol to a higher molecular weight alcohol in which the number of carbon atoms per molecule is a nonintegral multiple of the number of carbon atoms per molecule of the lower molecular weight alkanol, which process comprises contacting said alkanol with soda-lime at a temperature from 375 to 580 C. and a pressure from 0 to 1000 p. s. i.

2. A process for condensing two molecules of a normal l-alkanol having 11. carbon atoms per molecule to obtain a higher-boiling alcohol containing 2n-1 carbon atoms per molecule, n being aninteger in the range 2 to 10, which process comprises contacting said alkanol, in the vapor phase, with soda-lime at a temperature from 375 to 580 C., a pressure from 0 to 1000 p. s. i., and a charge rate from 1 to moles of alkanol Number 10 per kilogram soda-lime per hour, and recovering said higher-boilingalcohol as a product of the processn 3. The process of claim 2 in which the sodalime iscalcium hydroxide containing 0.2 to 30 weight percent of angalkali-metal hydroxide, 0.1-to 5 weight per cent silica, and not more than 20 weight per cent magnesiumhydroxide. 4. The. process pf .claim 3 in which the alkalimetal hydroxide-, is sodium hydroxide and the proportion thereof is from 0.5 to 10 weight per cent 5. The process of claim 2 in which the normal .l -alkanol,islepropanol, the higher-boiling alcohol isB-pentanoh, and the soda-lime is calcium hydroxidacontaining about 1 weight per cent. magnesium-hydroxide, 0.7 weight per cent sodium-hydroxide, and;0.6 weight per cent silica.

6. The processof claim 2 in which the l-alkanol is nl -octanol the higher-boiling alcohol is 8- ;pentadecanol,-;thetemperature is 400 C., and the pressure is 600 p. s. 'i.

7. A method for the condensation of a primarygaliphatic alcoholwhich comprises contacting a normal primary aliphatic alcohol containing from two to ten carbon atoms per molecule with soda-lime in admixture with copper oxidechromium oxide at a temperature within the range of 300 to 400 C., to produce, as one of the reaction products, an alcohol containing one less than twice the number of carbon atoms in said primary aliphatic alcohol.

8. The method which comprises contacting normal propanol with a contact material comprising soda-lime and copper oxide-chromium oxide as the essential ingredients at a temperature within the range of 300 to 400 C., passing the resulting efiiuent into contact with Raney nickel at a temperature within the range of 25 to C. and a pressure within the range of 200 to 1000 pounds per square inch, separating hydrogen gas from the thus-produced eiiiuent, passing at least a portion of the thus-separated hydrogen gas into contact with said Raney nickel along with the effluent from the first-named contacting step, and recovering diethyl carbinol and 2-methylpentanol-1 as products of the process.

9. A method for the condensation of a primary aliphatic alcohol which comprises contacting a primary aliphatic alcohol containing from two to ten carbon atoms per molecule with soda-lime at a temperature within the range of 400 to 580 C. at a pressure within the range of 200 to 1000 pounds per square inch to produce as a reaction product an alcohol containing one less than twice the number of carbon atoms in said primary aliphatic alcohol.

10. A process which comprises contacting a normal l-alkanol having from 2 to 10 carbon atoms per molecule with a contact material comprising soda-lime at a temperature from 375 to 580 C. and a pressure from 200 to 1000 p. s. i. to produce a higher-boiling alcohol and hydrogen, recovering said higher-boiling alcohol, and recycling said hydrogen to the contacting step.

11. A process for converting a normal l-alkanol to a higher molecular weight alcohol, which comprises contacting said alkanol, together with a second alkanol, with soda-lime at a temperature from 375 to 580 C. and a pressure of 200 to 1000 p. s. i. and recovering a product alcohol having a number of carbon atoms per molecule that is one less than the sum of the number of carbon atoms per molecule of the reactant alkanols.

12. The process of claim 11 in which said 1- alkanol has from 2 to 10 carbon atoms per molecule, and said second alkanol is a branched-chain alkanol having not more than 10 carbon atoms per molecule.

13. A process which comprises intercondensing a normal l-alkanol having from 2 to 10 carbon atoms per molecule with another alcoholselected from the group consisting of l-alkanols having 2 to 10 carbon atoms per molecule and benzyl alcohol and its homologues having 7 to 10 carbon atoms per molecule in the presence of soda-lime at a temperature from 375 to 580 C. and a pressure of 200 to 1000 p. s. i.

14. The process of claim 13 in which said normal l-alkanol is l-propanol, said other alcohol is benzyl alcohol, the temperature is 400 C., the pressure is 40 atmospheres, and 2-benzy1-1 -propanol is recovered as a product of the process.

15. The process of claim 13 in which the normal 1-a1kanol is l-propanol, said other alcohol is l-octanol, the temperature is 400 C., the pressure is 40 atmospheres, and 3-decano1 is recovered as a product of the process.

16. The process of claim 13 in which said normal l-alkanol is 1-propano1, said other alcohol is 2-methyl-l-propanol, the temperature is 400 C., the pressure is 40 atmospheres, and Z-methyl- 3-pentanol is recovered as a product of the process.

1'7. A process which comprises contacting normal propanol with a contact material comprising calcium hydroxide at a temperature in the range 375 to 580 C., a pressure in the range of 0 to 1000 p. s. i., and a charge rate in the range 1 to 15 mole. of propanol per kilogram of contact mass per hour and recovering 3-pentanol as a product of the process.

EDWARD E. BURGOYNE.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A PROCESS FOR CONVERTING A LOWR MOLECULAR WEIGHT, NORMAL, PRIMARY ALKANO TO A HIGHER MOLECULAR WEIGHT ALCOHOL IN WHICH THE NUMBER OF CARBON ATOMS PER MOLECULE IS A NONINTEGRAL MULTIPLE OF THE NUMBER OF CARBON ATOMS PER MOLECULE OF THE LOWER MOLECULAR WEIGHT ALKANOL, WHICH PROCESS COMPRISES CONTACTING SAID ALKANOL WITH SODA-LIME AT A TEMPERATURE FROM 375* TO 580* C. AND A PRESSURE FROM 0 TO 1000 P.S.I.
 13. A PROCESS WHICH COMPRISES INTERCONDENSING A NORMAL 1-ALKANOL HAVING FROM 2 TO 10 CARBON ATOMS PER MOLECULE WITH ANOTHER ALCOHOL SELECTED FROM THE GROUP CONSISTING OF 1-ALKANOLS HAVING 2 TO 10 CARBON ATOMS PER MOLECULE AND BEZYL ALCOHOL AND ITS HOMOLOGUES HAVING 7 TO 10 CARBON ATOMS PER MOLECULE IN THE PRESENCE OF SODA-LIME AT A TEMPERATURE FROM 375* TO 580* C. AND A PRESSURE OF 200 TO 1000 P.S.I. 